KR20060012608A - Fast crystallizing polyester compositions - Google Patents

Abstract

Fast crystallizing polyester compositions comprise a semicrystalline isotropic polyester, and specified amount of a liquid crystalline polymer, a solid particulate material, and a plasticizer for the isotropic polyester. These compositions generally crystallize faster and/or more extensively and/or at lower temperatures than the corresponding compositions without these ingredients present. The compositions are especially useful for molded and extruded parts.

Description

Fast Crystallized Polyester Composition {FAST CRYSTALLIZING POLYESTER COMPOSITIONS}

The fast crystallized polyester composition of the present invention comprises an isotropic polyester, a liquid crystal polymer, optionally a solid particulate material, and a plasticizer for the isotropic polyester.

Thermoplastic isotropic polyesters (IPE) are commercially important articles and are used for fibers, molded and extruded parts, foams and other applications. Many of these IPEs are semicrystalline, ie, some of the IPEs exist in crystalline form in the end-use parts. In semicrystalline polymers generally a portion of the polymer is present in amorphous (often glassy) form, and a portion of the polymer is present as crystallites and is usually distributed throughout the polymer. In most cases, IPE that can be crystallized is preferably used in semicrystalline form, and it is often helpful or necessary for the IPE to crystallize relatively quickly for the formation of the final part.

For example, in injection molding of thermoplastics, the molten polymer is injected into a mold and cooled quickly until it becomes a solid. The mold is then opened and the solid part is removed from the mold. If the part is not solid (or not) and easily deforms upon release from the mold, it may be deformed and thereby become useless. An important aspect in obtaining relatively strong parts from semicrystalline IPE is that they crystallize (at least partially) when removed from the mold. However, some semicrystalline IPEs crystallize very slowly and therefore must be in the mold for a long time to allow them to release without significant deformation. This lengthens the molding cycle and eventually becomes very undesirable and uneconomical.

To address this slow crystallization of some IPEs, so-called "crystallization packages" or "crystallization initiator systems" have been developed for slow crystallization polyesters. Such packages make crystallization initiation much faster and / or speed up the crystallization itself and / or lower the crystallization temperature. For example, poly (ethylene terephthalate) (PET) is a slow crystallization IPE and itself is not suitable for injection molding because of the very long molding cycle and / or the high mold temperature required. However, crystallization packages have been developed for this IPE, which are suitable for injection molding and other molding processes. Typical crystallization packages for PET are sodium ion raw materials such as sodium salt containing polymers of sodium or carboxylate and small amounts of plasticizer for PET. See, eg, US Reissue Patent No. 32,334. Not all IPEs crystallize slowly, but faster crystallization results in shorter melt processing cycle times, which is more desirable.

U. S. Patent No. 6,221, 962 describes a composition containing a liquid crystal polymer (LCP), a toughening agent with reactive functional groups, and a thermoplastic. The presence of specific compositions containing plasticizers is not mentioned.

U.S. Patent 4,753,980 describes polyester compositions containing certain toughening agents. The use of LCP is not mentioned in the patent.

US Pat. Nos. 4,438,236 and 4,433,083 describe combinations of LCPs with various thermoplastics. There is no particular mention of compositions containing polyesters and / or plasticizers.

SHKim et al., J. Appl. Polym. Sci., Vol. 67, p. 1383-1392 (1998) record that “10 wt% added liquid crystal polymer reinforcement accelerates the crystallization rate of PET”. have. There is no mention of the use of plasticizers in such compositions.

Summary of the Invention

The present invention

(a) about 35% or more by weight of semicrystalline isotropic polyester (IPE) having a melting point of about 100 ° C. or higher;

(b) a liquid crystal polymer (LCP) drug having a melting point of at least 50 ° C. higher than the cold crystallization point (CCP) of the isotropic polyester, or a melting point of at least about 150 ° C. if the isotropic polyester does not have a cold crystallization point. 0.1 to about 40 weight percent;

(c) 0.0 to about 60 weight percent of solid particulate material; And

(d) from about 0.2 to about 15 weight percent of a plasticizer for said isotropic polyester,

weight percent of (a) and (c) is based on the weight of the total composition, and weight percent of (b) and (d) is based on the weight of (a) in the composition.

In addition, the present invention

(a) about 35% or more by weight of semicrystalline isotropic polyester having a melting point of about 100 ° C. or higher;

(b) about 0.1 to about 40 weight percent of a liquid crystal polymer having a melting point of at least 50 ° C. higher than the cold crystallization point of the isotropic polyester, or a melting point of at least about 150 ° C. if the isotropic polyester does not have a cold crystallization point. ;

(c) 0.0 to about 60 weight percent of solid particulate material; And

(d) from about 0.2 to about 15 weight percent of a plasticizer for the isotropic polyester, wherein the weight percent of (a) and (c) is based on the weight of the total composition and the weight of (b) and (d) % Relates to cooling a composition based on the weight of (a) in the composition, from a temperature above the melting point of the isotropic polyester to a temperature below the melting point. will be.

Preferred compositions for this method are also preferred for the compositions (self) described above.

Certain terms are used herein and some of these are defined below.

"Liquid crystal polymer" means a polymer that is anisotropic when tested using the TOT test or its reasonable strain test, as described in US Pat. No. 4,118,372, which is incorporated herein by reference. Useful LCPs include polyesters, poly (ester-amides) and poly (ester-imides). One preferred form of LCP is “fully aromatic” where all groups in the polymer backbone are aromatic (except for linking groups such as ester groups), but non-aromatic side groups may be present.

"Isotropic" herein means a polymer that is isotropic when tested by the TOT test as described above. LCP and isotropic polymers are mutually exclusive species. Preferably, IPE is a continuous phase in the composition. This can be determined by a microscope in the appropriate form.

"IPE" means a condensation polymer that is isotropic and is an ester group with more than 50 percent of the groups linking repeat units. That is, the IPE can include polyesters, poly (ester-amides) and poly (ester-imides) as long as more than half of the linking groups are ester groups. Preferably, at least 70% of the linking groups are esters, more preferably at least 90% of the linking groups are esters, particularly preferably essentially all of the linking groups are esters. The proportion of ester linking groups can be calculated as a first order approximation by the molar ratio of the monomers used to form the IPE.

Unless otherwise noted, the melting point is measured by ASTM method D3418 using a heating rate of 10 ° C./minute. The melting point is taken at the maximum of the melting endotherm and measured at the first heating. If more than one melting point is present, the melting point of the polymer takes the highest value of the melting point. Except for LCP, the melting point preferably has a heat of fusion of at least 3 J / g associated with the melting point. The melting point of the LCP is taken at the second heating.

As used herein, with respect to components in a composition, including a), b), c) and d), the singular expressions such as "IPE" or "granular solids" also mean a plural and satisfy the constraints described herein. There may be more than one of them.

By “granular solids” is meant a solid (which is insoluble at temperatures to which the composition is normally exposed) which has been separated finely enough to disperse in the composition under melt mixing conditions (see below). Typically, particulate solids are materials that may already be used in thermoplastic compositions, such as pigments, reinforcing agents and fillers. The granular solid may or may not have a coating thereon, such as a sizing agent, to improve the adhesion of the particulate solid to the polymer of the composition. Granular solids can be organic or inorganic. Useful granular solids include minerals such as clay, talc, wollastonite, mica and calcium carbonate; Glass in various forms such as fibers, ground glass, hollow or hollow spheres; Carbon as black or fiber; Titanium dioxide; Aramid in the form of short fibers, fibrils or fibrids; And flame retardants such as antimony oxide, sodium antimonate and suitable insoluble organic compounds. Preferred particulate solids are wollastonite, mica, talc, glass, in particular glass fibers and calcium carbonate.

"CCP" means the value determined as follows. A composition containing IPE or IPE using a mold having a temperature of 50 ° C. is "pure" (there is no other component in the composition other than small amounts of materials such as antioxidants that may be needed to stabilize the IPE in the injection molding process) Injection molding into 1.59 mm (1/16 ") platelets. Appropriately sized samples (for devices) from platelets are placed on a differential scanning calorimeter (DSC) and 10 ° C / min from ambient temperature (approximately 20 to 35 ° C). The exothermic peak from the crystallization of IPE is taken as CCP during heating, if there is no crystallization exotherm below the melting point of IPE, the IPE does not have CCP.

The CCP can be determined by the "quick quench" method. In this method, pure IPE or a composition containing IPE is molded into sample bars. The sample from the sample rod is placed in a DSC pan and quickly heated to above the melting point of the material (usually about 270 ° C. for PET) and then quickly quenched in a dry ice / acetone mixture or liquid nitrogen. The material is then placed in DSC and equilibrated to 0 ° C. The temperature is then increased to 290.0 ° C. at 10.0 ° C./min. During heating, the exothermic peak from the crystallization of IPE is taken as CCP. If there is no crystallization exotherm below the melting point of the IPE, the IPE does not have a CCP.

For all semicrystalline polyesters as well as polyesters that are difficult to crystallize, lowering of CCP from CCP of pure polymers is generally recognized by those skilled in the art as indicating the presence of a crystallization initiation system. For a given amount of crystallization initiator system, the lower the CCP, the more efficient the crystallization initiator system is. The response to the amount of crystallization initiator system is generally limited and higher amounts provide less or no benefit (little or no effect on lowering of CPP).

By "plasticizer" is meant a compound or mixture of compounds that typically has a melting point of about 50 ° C. or less with a (average) molecular weight of 2000 or less. The plasticizer may be an oligomer, in which case its number average molecular weight (measured by size exclusion chromatography using appropriate standards) is 2000 or less. These are the typical properties of plasticizers. For further explanation of plasticizers, see CECarraher, Jr., Seymour / Carraher's Polymer Chemistry, Fifth Edition, Marcel Dekker Inc., New York, 2000, pages 60 and 463-465, incorporated herein by reference. See the

"All weight percentages are based on all components in the composition" means that the percentage of the total of (a), (b), (c) and (d) + any other components present in the composition It means based on quantity.

The IPE used may be any IPE with the required melting point. Preferably, the melting point of the IPE is at least about 150 ° C, more preferably at least about 200 ° C. Polyesters (most or all ester linking groups) are usually derived from one or more dicarboxylic acids and one or more diols. In one preferred type of IPE, the dicarboxylic acid comprises at least one of terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid, and the diol component is HO (CH ₂ ) _n OH (I), 1,4- Cyclohexanedimethanol, HO (CH ₂ CH ₂ O) _m CH ₂ CH ₂ OH (II) and HO (CH ₂ CH ₂ CH ₂ CH ₂ O) _z CH ₂ CH ₂ CH ₂ CH ₂ OH (III) , n is an integer from 2 to 10, m is on average from 1 to 4 and z is on average from about 7 to about 40. Note that (II) and (III) may be m and z respectively changed and thus m and z are averages and they may be mixtures of compounds which are not integers. In preferred polyesters, n is 2, 3 or 4 and / or m is 1.

Specific preferred IPEs are poly (ethylene terephthalate) (PET), poly (1,3-propylene terephthalate) (PPT), poly (1,4-butylene terephthalate) (PBT), poly (1,4-butyl Ethylene terephthalate) and thermoplastic elastomeric polyesters with poly (tetramethyleneether) glycol blocks ⁽ obtained as Hytrel ^(R) from E.I.Dupont Nemoir & Company, Wilmington, Delaware, 19898, USA ⁾ . Available) and poly (1,4-cyclohexyldimethylene terephthalate) (PCT), with PET being particularly preferred. “PET” herein means that at least 80, more preferably at least 90 mole percent of the diol repeat units are derived from ethylene glycol, and at least 80, more preferably at least 90 mole percent of the dicarboxylic acid repeat units are derived from terephthalic acid. Refers to the polyester. If there is more than one IPE (with the appropriate melting point), all of these polymers in the composition are considered as component (a).

Preferably, the solid particulate material is 0.2 to 60% by weight of the total composition, more preferably about 5 to about 50% by weight of the total composition.

Preferably the IPE is at least about 40% by weight of the total composition, more preferably at least about 50% by weight of the total composition.

Preferably the LCP is about 0.5 to about 20, more preferably about 1.0 to about 10 weight percent of (a). Also preferably the LCP is a discontinuous phase (as measured by an appropriately shaped microscope-it is assumed that it exists as a dispersed phase if the particle size of the LCP is too small to be observed under an electron microscope).

Preferably, the plasticizer is about 0.5 to about 12 weight percent of IPE [(a)], more preferably about 3.0 to about 10% of IPE. One preferred type of plasticizer is a diester of a diol of formula R ¹ CO ₂ R ² O ₂ CR ¹ (wherein each R ¹ is independently hydrocarbyl containing 1 to 20 carbon atoms, more preferably Is alkyl, and each R ² (what R ² means in each molecule may vary slightly) is alkylene optionally substituted with an ether group containing 2 to 30 carbon atoms. By alkylene is meant a divalent hydrocarbyl radical (containing in carbon and hydrogen phase) in which the free valence is at two different alkyl (saturated) carbon atoms. Specific useful plasticizers include poly (ethylene glycol 400) di-2-ethylhexanoate and poly (ethylene glycol) dilaurate having a number average molecular weight of about 946. Other useful plasticizers can be found in US Reissue Patents 32,334 and 548,978, which are incorporated herein by reference. Plasticizers useful for one particular IPE are not necessarily useful for other IPEs, but often this will be an example.

Other components, particularly those commonly used in thermoplastics, may be added to the composition in amounts commonly used in thermoplastics. Such materials include antioxidants, lubricants, mold release agents, flame retardants, (paint) adhesion promoters, other types of polymers (to form polymer blends), and the like. Preferably, all of all the components are less than about 60%, more preferably less than about 40%, particularly preferably less than 25% by weight of the composition.

Preferred optional components are polymer toughening agents. It is typically an elastomer and a polymer with a relatively low melting point of generally less than 200 ° C., preferably less than 150 ° C., with functional groups attached thereto capable of reacting with IPE (and optionally other polymers present). Since IPEs usually have carboxyl and hydroxyl groups present, these functional groups can usually react with carboxyl and / or hydroxyl groups. Examples of such functional groups include epoxy, carboxylic anhydride, hydroxyl (alcohol), carboxyl and isocyanato. Preferred functional groups are epoxy and carboxylic anhydride, with epoxy being particularly preferred. Such functional groups are usually "attached" to the polymer toughening agent by grafting small molecules onto the polymer already present, or by copolymerizing monomers containing the desired functional groups when the polymer toughening molecules are made by copolymerization. As an example of grafting, maleic anhydride may be grafted onto hydrocarbon rubbers using free radical grafting techniques. The grafted polymer obtained has carboxylic anhydride and / or carboxyl groups attached thereto. An example of a polymer toughening agent in which a functional group is copolymerized in a polymer is a copolymer of ethylene and a (meth) acrylate monomer containing a suitable functional group. (Meth) acrylate herein means that the compound may be an acrylate, methacrylate or a mixture of both. Useful (meth) acrylate functional compounds include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate. In addition to ethylene and functional (meth) acrylate monomers, other monomers such as vinyl acetate, unfunctionalized (meth) acrylate esters such as ethyl (meth) acrylate, n-butyl (meth) acrylate and cyclohexyl (meth ) Acrylate may be copolymerized into a polymer. Preferably, the amount of polymer toughening agent containing functional groups present is (a) from about 2 to about 40 weight percent of IPE. Preferred toughening agents include those described in US Pat. No. 4,753,980, which is incorporated herein by reference. Particularly preferred toughening agents are ethylene, ethyl acrylate or copolymers of n-butyl acrylate and glycidyl methacrylate.

It is preferred that the polymer toughening agent contains from about 0.5 to about 20 weight percent functional group containing monomer, preferably from about 1.0 to about 15 weight percent, more preferably from about 7 to about 13 weight percent functional group containing monomer. There may be more than one type of functional monomer in the polymer toughening agent. The stiffness of the composition has been found to be increased by increasing the amount of polymer toughening agent and / or functional group. However, this amount is preferably not increased to the extent that the composition can be crosslinked, especially before the final part form is achieved. Preferably, from about 2 to about 30 weight percent, more preferably from about 5 to about 25 weight percent, particularly preferably from about 10 to about 20 weight percent polymer toughening agent is present in the composition.

When polymer toughening agents such as those described above are added, in many cases it has been found that the particle size of the LCP in the composition is significantly reduced. For example, the particle size of the LCP in one composition is about 2-5 μm, while the LCP particle size is about 0.2-0.5 μm in the same composition except that it contains a polymer toughening agent.

Preferred types of other components are epoxy compounds or resins. Preferably such compounds or resins have an average molecular weight of less than about 1000 (even though they contain epoxy groups, polymer tougheners such as those described above are not considered herein as part of an epoxy compound or resin). Such epoxy materials are preferably present at levels of 0.1 to about 1.0 weight percent of the total composition. Useful epoxy compounds or resins include EPON ^(R) 1002F, 1009F or 1031, or Araldite ^(R) GT7099 or GT 6099. In some cases it is believed that the epoxy compound or resin stabilizes the melt viscosity and / or improves the color stability of the composition. The latter is particularly important when the exterior parts are not coated with paint or other coatings.

It is understood that the desired component and / or component amounts may be combined with other preferred components and / or component amounts therein.

In one preferred type of composition, less than 25 ppm, preferably less than 10 ppm of “free” metal cations such as alkali metal or alkaline earth metal cations are added to the composition. By "free" metal cation is meant a cation capable of easily reacting with a functional group present in the composition, such as a carboxyl group, to form a carboxylate salt. Free metal cations can be added as carboxylate salts, such as acetates of 4-hydroxybenzoate, as other metal salts such as metal halides, and as metal salts of polymer carboxylates. Common impurities in other components, or metal cations tightly bound to components or minerals that are part of minerals or other compounds, are not included in the added free metal cations. As mentioned above, some of the crystallization initiation systems for polyesters contain alkalis or other metal cations. They are sometimes harmful to using such compositions for electrical or electronic applications, where metal ions can change the electrical properties of the composition. Similarly, the presence of metal cations can make hydrolysis or other chemical resistance problems worse. This disadvantage is not clear in the present composition. In addition, at least some of the polymeric tougheners are more effective or effective in smaller amounts, especially when the metal cation is absent or only in small amounts, particularly when counterions to the metal cations may react with functional groups that are part of the polymeric toughener. I think. Therefore, a combination of low metal ion content and the presence of a polymer toughening agent is preferred.

The compositions described herein can be prepared by typical melt mixing techniques. For example, the components can be added to a single or twin screw extruder or kneader and mixed in a conventional manner. Preferably, the temperature of the components in at least part of the mixing device is at or above the melting point of the LCP present (the temperature measured or set in the zone of the mixing device may be lower than the actual material temperature due to mechanical heating). After mixing the materials, they may be formed into suitable pellets or other particles to feed the melt molding machine. For thermoplastics, melt molding can be carried out by conventional methods such as injection molding, thermoforming or extrusion, or a combination thereof. Some components may be used to reduce the consumption of solids, such as fillers, and / or to improve dispersion, and / or to reduce the thermal history of relatively thermally labile components, and / or to reduce losses due to evaporation of volatile components. For example, fillers, plasticizers and lubricants (release agents) may be added at one or more downstream points in the extruder.

As mentioned above, parts of the compositions of the present invention may be made by heating the composition above the melting point of the IPE (and thus melting the IPE) and then cooling them below the melting point to solidify the composition and form molded parts. . Preferably, the part is cooled to at least 50 ° C. below the melting point, more preferably below at least 100 ° C., or preferably below CCP below the melting point. Most commonly, the composition is finally cooled to ambient temperature, most typically 15 to 45 ° C.

The compositions described herein (often with the additional optional components present) are particularly useful as "appearance parts", ie parts where surface appearance is important. This may be applied depending on whether the surface of the composition is directly observed or whether it is coated with other materials such as paint or metal. Such parts may include automotive body panels such as wheel covers, dashboards, hoods, tank lids, and other exterior parts; Internal car panels; Equipment parts such as handles, adjustment panels, sashes, cleaning machine tubes and external parts, internal or external refrigerator panels, and dishwasher front or internal panels; Power tool housings such as drills and saws; Electronic cabinets and housings such as personal computer housings, printer housings, peripheral housings, server housings; Exterior and internal panels for trains, tractors, lawn mower wings, trucks, snowmobiles, aircraft, and ships; Decorative interior panels for buildings; Furniture such as office and / or home chairs and tables; And telephones and other telephone devices. As mentioned above, these parts may be painted, or they may be left uncolored in the composition.

The composition can be colored with pigments and / or dyes, and therefore many color variations are possible. This type of coloring of parts made from the composition is particularly economically attractive since these parts need not be subsequently coated (painted) in one or more additional steps. If extremely high gloss and / or image clarity is not required, this is often a better coating substitute. Alternatively, parts made of such compositions may be coated (painted).

Another method of coloring the surface of parts (or variants thereof) made from such compositions is the dye sublimation (printing) method.

As mentioned above, the compositions of the present invention or variants thereof may be used for automobile parts, in particular for automobile bodies. Currently, three different approaches exist for producing coated automotive bodies assembled into a mixed structure from metal and plastic parts.

1. A method known as an off-line process, in which the metal body and the plastic part are coated separately and then assembled.

A disadvantage of the off-line process is that, at least in the case of a direct visual comparison of the coated plastic part and the coated metal part for reasons of construction, for example, the coated parts are actually seamlessly close and / or coated parts. Due to the arrangement on this one side, it is easy to lack visual coordination of the coated metal and plastic surfaces.

A further disadvantage is the need to operate two coating lines.

2. In-line, which assembles a metal body already provided with an electrodeposition coating as a primer and an uncoated plastic component or optionally a plastic component provided with only a plastic primer and provides one or more additional coating layers in subsequent coating processes ( a method known as an in-line process.

A disadvantage of the in-line process is that the assembly step is inserted into the coating process as an interfering intermediate step, which involves the risk of introducing contaminants into further coating processes.

3. Known as an on-line process in which an uncoated car body and an uncoated plastic part made of metal, or a plastic part optionally provided only with a plastic undercarriage, are assembled into a car body composed of a mixed structure and then passed through a general coating process including electrodeposition coating. In this method, the electrodeposited coating is naturally provided only to the electrically conductive metal part, while all the coating layers applied in succession are applied to both the electrodeposited coated metal part and the plastic part.

The on-line process is particularly preferred because it clearly separates the body basic shell configuration and coating process and does not disrupt the coating order.

Basically, because high temperatures are used in the drying of electrodeposited coatings, plastic materials that are only adequately heat-resistant and at the same time heat-strain-resistant are suitable for particularly preferred on-line processes.

The coated substrate body is assembled from metal parts with visible metal and plastic surfaces and at least one plastic part (the compositions described herein) in the following successive steps:

(1) electrodepositing the substrate, removing the non-deposition electrodeposition coating from the substrate and thermally crosslinking the deposited electrodeposition coating thereby forming an electrodeposition coating primer on the metal surface,

(2) Apply and cure at least one additional coating on at least all of the visible metal and plastic surfaces, wherein the at least one plastic part forms the visible plastic surface of the substrate with the composition described herein.

When coating them, the plastic parts (of the compositions described herein) can be pretreated in a conventional manner, for example by UV irradiation, fume treatment or plasma treatment, or conventional plastic primers, in particular known to those skilled in the art, in particular Prior to assembly with the metal part, it may be coated with a conductive primer which provides the plastic part with the appropriate electrical conductivity for electrostatically-assisted coatability.

Substrate coated by the method according to the invention by assembling metal parts and at least one plastic part, optionally provided with a plastic primer, by conventional methods known to those skilled in the art, for example by screwing, clipping and / or attaching To form.

The plastic part (s) of the substrate with the smallest possible connection width and in particular on the same side as the adjacent metal parts are assembled with at least the metal parts.

Optionally, if there are additional plastic parts that are generally different in composition from the at least one plastic part and are less resistant to thermal deformation, they are fitted after completion of step (1) of the process according to the invention and further coating steps (2) and / or (compare with the in-line method described above), and after completion of the method according to the invention it can be fitted into the final coated form (compare with the off-line method described above). .

In terms of the application of at least one further coating layer, which takes place in step (2) of the method according to the invention, preferably by electrostatically-assisted spray coating, the metal and plastic part (s) are removed so that they It is convenient to assemble; For example, direct electrical contact between the conductive primer and the metal can be by direct contact or via an electrically conductive connecting element, for example a metal screw.

In order to create an anti-corrosion primer layer on the metal part, the substrate assembled from the metal part and the at least one plastic part in step (1) of the method according to the invention is subjected to an electrodeposition coating bath in a conventional manner known to those skilled in the art. Coating.

Suitable electrodeposition coatings include, for example, conventional aqueous coating compositions having a solids content of 10 to 30% by weight.

The electrodeposition coating composition may be a conventional anode electrodeposition coating known to those skilled in the art. The binder base of the anode electrodeposition coating composition may be selected as follows. Examples of anode electrodeposition binders are polyester, epoxy resin esters, (meth) acrylic copolymer resins, for example corresponding to weight average molecular weights (Mw) of 300 to 10000 and acid values of for example 35 to 300 mg KOH / g. Melanie oil or polybutadiene oil with carboxyl group content. At least a portion of the carboxyl groups are converted to carboxylate groups by neutralization with a base. Such a binder may be crosslinked by itself or by a separate crosslinking agent.

Preferably, conventional cathode electrodeposition coatings known to those skilled in the art are used in the process according to the invention for the application of electrodeposition coating layers. The cathode electrodeposition coating composition contains a binder having a cationic group or a group that can be converted to a cationic group, for example a basic group. Examples thereof include amino, ammonium, for example quaternary ammonium, phosphonium and / or sulfonium groups. Nitrogen-containing basic groups are preferred. The groups may be present in tetrameric form or they are converted to conventional neutralizing agents such as organic monocarboxylic acids such as formic acid, lactic acid, methane sulfonic acid or acetic acid and cationic groups. Examples of basic resins are, for example, those having primary, secondary and / or tertiary amino groups corresponding to amine numbers in the range of 20 to 200 mg KOH / g. The weight average molecular weight (Mw) of the binder is preferably 300 to 10,000. Examples of such binders are amino (meth) acrylic resins, aminoepoxy resins, aminoepoxy resins with terminal double bonds, aminoepoxy resins with primary OH groups, aminopolyurethane resins, amino group-containing polybutadiene resins or modified epoxy resins. Carbon monoxide-amine reaction product. Such binders may be self-crosslinked or may be used with known crosslinking agents in the mixture. Examples of such crosslinkers include aminoplastic resins, blocked polyisocyanates, crosslinkers with terminal double bonds, polyepoxy compounds or crosslinkers containing transesterable groups.

Apart from the binder and the separate crosslinker, the electrodeposition coating composition may contain pigments, fillers and / or conventional coating additives. Examples of suitable pigments include conventional inorganic and / or organic colored pigments and / or fillers such as carbon black, titanium dioxide, iron oxide pigments, phthalocyanine pigments, quinacridone pigments, kaolin, talc or silicon dioxide. Examples of additives include, in particular, wetting agents, neutralizing agents, leveling agents, catalysts, corrosion inhibitors, anti-cratering agents, antifoaming agents, solvents.

Electrodeposition coating takes place in a conventional manner known to those skilled in the art, for example at deposition voltages of 200 to 500V. After deposition of the electrodeposition coating, the excess electrodeposition coating that is stuck but not deposited from the substrate is rinsed in a conventional manner known to those skilled in the art, for example by washing with water. Thereafter, in order to crosslink the electrodeposition coating, the substrate is fired at an oven temperature of, for example, 220 ° C or lower, depending on, for example, a target temperature of 200 ° C or lower.

In a subsequent step (2) of the process according to the invention, at least one further coating layer is preferably electrodeposited coating so obtained and fired onto the metal surface, preferably by spray application, in particular by electrostatically assisted spray application. The layer only applies to all visible metal and plastic surfaces provided.

If only one additional coating layer is applied, this is generally a colored top coat. However, it is desirable to apply one or more additional coating layers. Examples of conventional multicoat structures formed from multiple coating layers are as follows:

-Undercoat Surface Treatment / Top Coat

-Undercoat Surface Treatment / Basic Coat / Clear Coat

-Basic coat / clear coat

-Substituent surface treatment agent replacement layer / base coat / clear coat

To provide surface protection for stone-sculpture protection and surface smoothing, and to provide protection against environmental influences, thereby providing a surface for decorative top coats, consisting of colored top coats or color- and / or effect-generating base coats and protective clear coats. To prepare, either a primer or a primer coating is used.

The multicoat structure, mentioned as an example in particular in providing high scratch-resistant, may also be provided on the entire surface or a part of the surface with a transparent sealing coat.

All the coating layers following the electrodeposition coating layer can be applied from conventional coatings known to those skilled in the art in order to apply the relevant coating layer. This may be for example a respective liquid coating containing water and / or an organic solvent as a diluent or powder coating. The coating can be a single-component or multi-component coating; They can be physically dried or can be crosslinked by oxidation or chemically. In particular, the primer coating, the top coat, the clear coat and the seal coat can be cured thermally (by convection and / or by infrared radiation) and / or by the action of energy-containing radiation, in particular ultraviolet radiation. Chemical crosslinking system.

If at least one coating layer is applied in step (2) of the method according to the invention, the coating layer should basically not be cured separately prior to the application of each coating layer. Rather, the coating layer can be applied according to the wet-on-wet principle known to those skilled in the art, where at least two coating layers are cured together. In particular, for example, in the case of the base coat and the clear coat, after the application of the base coat and optionally after a short flash-off step, the clear coat is applied and cured with the base coat.

The on-line method according to the invention is a mixture of metal parts and plastic parts, which are based on thermoplastics and coated to have an excellent balance of the visual influence of the coated plastic and the metal surface and are suitably resistant to thermal deformation. The board can be assembled.

Non-exterior parts can also be made with such compositions. These are the parts whose surface appearance is not important. Such parts include those made of so-called industrial thermoplastics, in particular those filled with materials designed to enhance the physical properties of the composition, such as stiffness, stiffness and tensile strength.

CCP carried out by either Method A which is injection molding into a 50 ° C. mold as described above or Method B which is a rapid quench method as described above.

Melting point Determined by ASTM D3418-82 at a heating rate of 10 ° C./min. The peak of the melting endotherm is regarded as the melting point.

Freezing Time Freezing time (sometimes called crystallization time) is defined as the curve point in the cavity pressure curve. In order to measure the cavity pressure over time during the molding cycle, a transducer placed behind the ejector pin located near the part's gate is used. At the start of the injection cycle, a time of zero seconds occurs when the screw starts to move forward. Peak pressure occurs when the part is fully charged and the pressure remains essentially constant during the beginning of the filling phase of the molding cycle. When the resin begins to crystallize, shrinkage occurs. Once the resin in the gate is fully crystallized, crystallization of the resin in the cavity causes sufficient shrinkage and a decrease in cavity pressure is shown. Joint pressure continues to drop over time. The point at which the curve transitions from concave to convex is a curved point and is defined as a freezing point.

Crystallization Half-Life (CHL) This was performed by differential scanning calorimetry (DSC) method. In one sample preparation method, the sample was simply used on its own. In another method, the sample was heated to 290 ° C., quenched and quenched in liquid nitrogen. Using either manufacturing method, the sample was heated to the desired temperature at a rate of 200 ° C./min, and crystallization exotherm occurred at that temperature in the DSC. From the exothermic curve generated over time, the crystallization half-life at this temperature was calculated.

Compounding and Forming Method

All polymer compositions were prepared by blending in a 30 mm Warner and Playler double screw extruder. All components are combined together, behind the extruder (Tab 1), except for side feed of nigloss ^(R) and other minerals into the canister 5 (of 10 canisters ⁾ and the addition of a plasticizer using a liquid infusion pump. Added. Note the exception to this method in embodiments. The cylinder temperature is set at 280-310 ° C., depending on the composition and the extruder speed and the rpm of the screw, resulting in a melting point of 290-350 ° C.

The resin was molded into ASTM test specimens on a 3 or 6 ounce injection molding machine. Melting temperature was 280-300 degreeC, and mold temperature was 110-130 degreeC.

In the examples, specific components are used and they are defined as follows:

CaCO ₃ -Granular Calcium Carbonate, Superflex ^(R) 200 (available from Mineral Technologies Inc., New York, 10174, USA)

Krista ^(R) 3934-PET homopolymer, IV = 0.67 (available from E.I.Dupont Nemoir & Company, Inc., Wilmington, Delaware, USA, 19898)

Fiberglass-PPG3563 (available from PPG Industries, Pittsburgh PA, USA 15272)

Irganox ⁽¹⁰⁾ -antioxidant (available from Ciba Specialty Chemicals, Tarrytown, NY 10591)

LCP1-50/50/70/30/320 (molar ratio) hydroquinone / 4,4'-biphenol / terephthalic acid / 2,6-naphthalene dicarboxylic acid / 4-hydroxybenzoic acid copolymer, melting point 334 ° C

Licowax ^(R) PED 521-Oxidized Polyethylene Wax Used as Mold Lubricant (available from Clariant Corporation, D-65840 Schlesbach am Towns, Germany)

Niard ^(R) 1250-unpolished wollastonite fiber (available from Nico Minerals, Calgary, Canada AB)

Nigros ^(R) 4-average approximately 9 μm long wollastonite fiber, untreated with sizing agent (available from Nico Minerals, Calgary, Canada AB)

Nigloss ^(R) 4W 20544-wollastonite fibers treated with sizing agent, on average approximately 10 μm long (available from Nico Minerals, Calgary, AB, Canada)

Plastol ^(R) 809-Polyethylene glycol 400 di-2-ethylhexanoate

Polymer A-ethylene / n-butyl acrylate / glycidyl methacrylate (66.75 / 28 / 5.25 wt%) copolymer, melt index 12 g / 10 min

Polymer B-ethylene / n-butyl acrylate / glycidyl methacrylate (66/22/12 wt%) copolymer, melt index 8 g / 10 min

RCL 4-Thiona ^(R) RCL 4 Chloride process rutile-type TiO ₂ surface-treated with titanium dioxide, alumina and organic materials (Available from SMC Corporation, Baltimore, Midland, USA).

Talc-Jetfil ^(R) 575C (available from Luzenac America, Eaglewood ^, 80112, USA).

In the examples, all composition amounts shown below are parts by weight. All compositions containing PET included 0.3 wt% Irganox ^(R) 1010 and 0.5 wt% PED521.

Example 1

The composition was made using standard methods. Method A was used to determine the CCP. The compositions and CCPs are shown in Table 1.

condition Krista ^(R) 3934 LCP1 Nigloss ^(R) 4W Plastol ^(R) 809 CCP, ℃ A 100.0 127.9 B 97.0 3.0 119.5 C 92.0 5.0 3.0 114.4 D 95.0 5.0 122.2 E 82.0 15.0 3.0 121.3 F 80.0 5.0 15.0 122.8

Example  2

The composition was made using standard methods. Method A was used to determine CCP. Table 2 shows the composition and CCP.

condition Krista ^(R) 3934 LCP1 Nigloss ^(R) 4W Plastol ^(R) 809 CCP, ℃ A 87.0 0.0 10.0 3.0 117.3 B 87.0 1.0 9.0 3.0 115.5 C 87.0 3.0 7.0 3.0 112.9 D 87.0 7.0 3.0 3.0 109.9 E 87.0 9.0 1.0 3.0 111.4 F 87.0 10.0 0.0 3.0 110.1

Example  3

The composition was made using standard methods. Each filler is present in an amount of 15 parts by weight. Apart from states C and D using method B, method A was used to determine CCP. The compositions and CCPs are shown in Table 3.

condition Krista ^(R) 3934 LCP1 Filler Plastol ^(R) 809 CCP, ℃ A 77.0 5.0 glass fiber 3.0 109.3 B 77.0 5.0 Niad ^(R) 1250 3.0 112.0 C 77.0 5.0 CaCO ₃ 3.0 105.7 D 77.0 5.0 RCL4 3.0 118.1 E 77.0 5.0 talc 3.0 116.3 F 77.0 5.0 Nigloss ^(R) 4 3.0 110.8

Example 4

The composition was made using standard methods. The polymer composition was molded using a melt temperature of 284-286 ° C., a mold temperature of 109-100 ° C., a cycle time of 39-40 seconds, a settling / filling pressure of 80 MPa and a filling rate of 19.1 mm / sec. Physical property tests were performed according to standard ISO methods. The freeze times shown are commercial PET injection molding resins containing 30% by weight glass fiber, Ryite® 530 BK503 (E.I.Dupont Nemoir & Company Inn, Wilmington, Delaware, 19898, USA ⁾ . Available from ^{Co., Ltd.)} and a crystallization package including sodium stock and Plastol ^(R) 809 but without polymers similar to Polymers A and B. Positive values indicate that the freezing time is longer than Linite ^(R) 530, while negative values indicate that the freezing time is shorter than Linite ^(R) 530. The compositions and results are shown in Table 4.

condition A B C D E F G Krista ^(R) 3934 81.2 61.2 71.2 71.2 75.2 65.2 56.2 LCP1 5 5 5 One One 10 Polymer B 15 5 5 15 15 Polymer A 5 Irganox ^(R) 1010 0.3 0.3 0.3 0.3 0.3 0.3 0.3 PED521 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Nigloss ^(R) 4W20544 15 15 15 15 15 15 15 Plastol ^(R) 809 3 3 3 3 3 3 3 Tensile strength, MPa 72.2 39.4 51.1 53.2 55.2 39.0 39.0 Tensile Elongation,% 2.9 27 7 10 12 35 25 Tensile Modulus, GPa 5.8 3.65 4.62 4.52 4.67 3.44 3.39 Flexural strength, MPa 130 76.6 102 103 106 76.6 73.7 Flexural Modulus, GPa 5.64 3.80 4.82 4.75 4.84 3.72 3.65 Approximate freeze time, seconds 2 -3 0 -0.5 0 -1.5 -3.5

Example  5

By melt mixing using a double screw extruder, a composition containing Crysta ^(R) 3934, Plastol ^(R) 809 and LCP1 is made, which compositions (“states”) are shown in Table 5 together with their components. CCP and CHL (at 110 ° C) in this state were measured, and the results are shown in Table 5. These indicate that the combination of LCP and plasticizer is very effective in nucleating and accelerating the crystallization of Crysta ^(R) 3934.

condition Krista ^(R) 3934 LCP1 Plastol ^(R) 809 CCP, ℃ CHL, min A 100.0 131.5 ° 4.87 minutes B 99.0 1.0 124.5 ° 3.28 minutes C 97.0 3.0 124.1 ° 2.98 minutes D 95.0 5.0 124.5 ° 2.28 minutes E 99.0 1.0 128.8 ° 5.08 minutes F 97.0 3.0 122.0 ° 1.68 minutes G 95.0 5.0 117.9 ° 0.98 minutes H 98.0 1.0 1.0 123.2 ° 2.48 minutes I 96.0 3.0 1.0 121.3 ° 1.77 minutes J 94.0 5.0 1.0 119.8 ° 1.62 minutes K 96.0 1.0 3.0 114.9 ° 1.22 minutes L 94.0 3.0 3.0 114.8 ° 0.88 minutes M 92.0 5.0 3.0 113.6 ° 0.75 minutes N 94.0 1.0 5.0 110.1 ° 0.67 minutes O 92.0 3.0 5.0 109.0 ° 0.55 minutes P 90.0 5.0 5.0 108.1 ° 0.40 minutes

Example  6

Preparation of Steel / Plastic Substrate: A 13 cm x 13 cm plastic panel made from the composition of State B of Example 4 was mounted on a 30 cm x 60 cm panel of body steel in a manner in which two common edges were formed, using double-sided adhesive tape. Stuck on. Prior to bonding, a conductive primer (2-component primer, conductive, R 82913, available from Dupont Performance Coatings GmbH & Co. KG, Wuppertal, Germany) was provided in the plastic panel to a dry film thickness of 15 μm.

Preparation of a cathode electrodeposition coating bath: 4356 g of an aqueous cathode electrodeposition binder dispersion (Herberts Aqua EC2000, R39660 from Dupont Performance Coatings GmbH & Co. KG, Wuppertal, Germany) was charged with 1408 g of cathode electrodeposition pigment paste (Herberts Aqua EC 2000, R39661 from DuPont Performance Coatings GmbH & Co., Wuppertal, Germany) and a cathode electrodeposition coating bath having a solids content of 18% by weight was prepared by dilution with 5236 g of deionized water.

Preparation of multilayer coatings: Cathode electrodeposition (CED) coating bath according to the example (coating conditions: 2 minutes at 30 ° C. at a deposition voltage of 320 V; firing conditions: 20 minutes at 175 ° C. object temperature) to a dry film thickness of 20 μm Steel / plastic substrates were coated. A steel / plastic substrate provided in this way with only a CED coating layer on the metal surface was dried with a 35 μm dry film with a white aqueous filler (Huberts Aqua-Peel R63520, DuPont Performance Coatings GmbH & Co.KG, Wuppertal, Germany). It was coated to a thickness, flashed off at 80 ° C. for 10 minutes, and fired at 160 ° C. (object temperature) for 25 minutes. Steel / plastic substrates coated over the entire surface with a layer of white aqueous filler, up to a dry film thickness of 12 μm, with a black metallic aqueous base coat (Huberts Aqua-Base R65949, DuPont Performance Coatings GmbH & Co., Upertal, Germany) After a 10 minute flash off at 80 ° C., followed by a two-component polyurethane clear coat (2K-Clear R40491, DuPont Performance Coating GmbH & Co. KG, Wuppertal, Germany). It was coated with a dry film thickness of 35 μm, flashed off at 23 ° C. for 5 minutes, and calcined at 135 ° C. (object temperature) for 20 minutes. All spray coatings were applied in each case in a vertical position to the steel / plastic substrate. All flash-off, drying and firing operations were performed in the horizontal position.

Simply visual evaluation did not actually show a noticeable difference in appearance (gloss, roughness) between the coated plastic and steel surfaces. BYK wavescan apparatus (For optimal surface characterization of painted surfaces, a "Wave Scan" (Byk-Gardner GmbH, D-82538 Guerrezide, Germany) can be used. The wave scan is an Orange Peel meter, which mimics the visual assessment of surface smoothness], where a single wave value of 21 is measured for coated plastic surfaces, while the value for coated steel surfaces It was six. This indicates that excellent coating surfaces are obtained on both steel and plastic substrates.

Claims (29)

(a) about 35% or more by weight of semicrystalline isotropic polyester having a melting point of about 100 ° C. or higher; (b) about 0.1 to about 40 weight percent of a liquid crystal polymer having a melting point of at least 50 ° C. higher than the cold crystallization point of the isotropic polyester, or a melting point of at least about 150 ° C. if the isotropic polyester does not have a cold crystallization point. ; (c) 0.0 to about 60 weight percent of solid particulate material; And (d) from about 0.2 to about 15 weight percent of a plasticizer for said isotropic polyester, the weight percent of (a) and (c) is based on the weight of the total composition, and the weight percent of (b) and (d) is based on the weight of (a) in the composition. The composition of claim 1, wherein the isotropic polyester has a melting point of about 200 ° C. or greater. 3. The method according to claim 1, wherein the isotropic polyester is a repeat unit derived from at least one of terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid and HO (CH ₂ ) _n OH, 1,4- Cyclohexanedimethanol, HO (CH ₂ CH ₂ O) _m CH ₂ CH ₂ OH and HO (CH ₂ CH ₂ CH ₂ CH ₂ O) _z CH ₂ CH ₂ CH ₂ CH ₂ OH (where n is from 2 to 10) Wherein m is an average of 1 to 4 and z is an average of about 7 to about 40). The method of claim 1, wherein the isotropic polyester is poly (ethylene terephthalate), poly (1,3-propylene terephthalate), poly (1,4-butylene terephthalate) or poly (1,4-cyclohexyldimethylene terephthalate). The composition of claim 1, wherein the plasticizer is about 3.0 to about 10 weight percent of the isotropic polyester. 6. The plasticizer of claim 1, wherein the plasticizer is of the formula R ¹ CO ₂ R ² O _w CR ¹ wherein each R ¹ is hydrocarbyl and each R ² is one or more ether groups. Optionally substituted and alkylene having 2 to 30 carbon atoms. The composition of claim 1, wherein said liquid crystalline polymer is from about 1.0 to about 10 weight percent of said isotropic polyester. The composition of claim 1, wherein the solid particulate material is about 5 to about 50 weight percent of the total composition. The composition of claim 1, further comprising a polymer toughening agent containing at least one type of functional group. 10. The composition of claim 9, wherein said functional group is an epoxy or carboxylic anhydride. The composition of claim 9 wherein said functional group is an epoxy. 12. The composition of claim 11, wherein said polymer toughening agent comprises repeating units derived from epoxy containing (meth) acrylate and ethylene. The composition according to any one of claims 1 to 12, further comprising an epoxy compound or a resin. 14. A composition according to any one of the preceding claims containing less than 25 ppm free metal cations. Exterior components comprising the composition of claim 1. The exterior part according to claim 15, which is colored with pigments. The exterior component of claim 15 coated. 18. The vehicle body panel according to claim 15, a component part, a power tool housing, an electronic cabinet or housing, an exterior or interior panel of a vehicle, a decorative interior panel of a building, comprising the composition of claim 1. , Furniture, or facade parts that are telephones or telephone equipment. (a) about 35% or more by weight of semicrystalline isotropic polyester having a melting point of about 100 ° C. or higher; (b) about 0.1 to about 40 weight percent of a liquid crystal polymer having a melting point of at least 50 ° C. higher than the cold crystallization point of the isotropic polyester, or a melting point of at least about 150 ° C. if the isotropic polyester does not have a cold crystallization point. ; (c) 0.0 to about 60 weight percent of solid particulate material; And (d) from about 0.2 to about 15 weight percent of a plasticizer for the isotropic polyester, wherein the weight percent of (a) and (c) is based on the weight of the total composition and the weight of (b) and (d) A method for forming a molded part from an isotropic polyester, wherein% comprises cooling the composition based on the weight of (a) in the composition to a temperature below the melting point at a temperature above the melting point of the isotropic polyester. The method of claim 19, wherein the isotropic polyester has a melting point of about 200 ° C. or greater. The method of claim 19 or 20, wherein the isotropic polyester is a repeat unit derived from at least one of terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid and HO (CH ₂ ) _n OH, 1,4- Cyclohexanedimethanol, HO (CH ₂ CH ₂ O) _m CH ₂ CH ₂ OH and HO (CH ₂ CH ₂ CH ₂ CH ₂ O) _z CH ₂ CH ₂ CH ₂ CH ₂ OH (where n is from 2 to 10) Wherein m is an average of 1 to 4 and z is an average of about 7 to about 40). The method of claim 19, wherein the isotropic polyester is poly (ethylene terephthalate), poly (1,3-propylene terephthalate), poly (1,4-butylene terephthalate) or poly (1,4-cyclohexyldimethylene terephthalate). The method of claim 19, wherein the plasticizer is about 3.0 to about 10 weight percent of the isotropic polyester. 24. The method of any one of claims 19 to 23, wherein the liquid crystalline polymer is about 1.0 to about 10 weight percent of the isotropic polyester. The method of claim 19, wherein the solid particulate material is about 5 to about 50 weight percent of the total composition. 26. The method of any one of claims 19-25, further comprising a polymer toughening agent containing one or more types of functional groups. 27. The method of claim 26, wherein said functional group is an epoxy. The method of claim 27, wherein the polymer toughening agent comprises repeating units derived from epoxy containing (meth) acrylate and ethylene. 29. The method of any of claims 19-28, wherein the composition contains less than 25 ppm free metal cations.